metal-organic papers
Acta Cryst.(2005). E61, m441±m442 doi:10.1107/S1600536805002515 Lei Gouet al. [Cu(C6H4NO3)(NO3)(C12H8N2)]
m441
Acta Crystallographica Section EStructure Reports Online
ISSN 1600-5368
(Nitrato-
j
O
)(1,10-phenanthroline-
j
2N,N
000)-(picolinato
N
-oxide-
j
2O,O
000)copper(II)
Lei Gou,aXiong-Wei Qu,bBo
Zheng,aDao-Yong Wangaand
Huai-Ming Hua*
aDepartment of Chemistry, Northwest University, Xi'an 710069, People's Republic of China, andbInstitute of Polymer Science and Engineering, School of Chemical Engineering, Hebei University of Technology, Tianjin 300130, People's Republic of China
Correspondence e-mail: chemhu1@nwu.edu.cn
Key indicators Single-crystal X-ray study
T= 298 K
Mean(C±C) = 0.003 AÊ
Rfactor = 0.034
wRfactor = 0.079
Data-to-parameter ratio = 14.2
For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.
#2005 International Union of Crystallography Printed in Great Britain ± all rights reserved
The coordination environment of copper(II) in the title compound, [Cu(C6H4NO3)(NO3)(C12H8N2)], is square pyra-midal; the basal plane comprises the two N atoms of 1,10-phenanthroline and the two O atoms of picolinate N-oxide, with the apical position occupied by a nitrate O atom.
Comment
Picolinic acidN-oxide has a polar N!O group that provides a strongly basic O-atom site for coordination. Only a few complexes of this ligand have been crystallographically authenticated. In the binuclear compound La(6-mepic-NO)66H2O, two LaIIIatoms are bridged by two picolinateN -oxide groups (Yanet al., 1995). In the ErIII±NaImixed-metal coordination polymer, the main feature is a polymeric chain of two zigzag chains (Mao et al., 1998). The copper(II) nitrate derivative of the acid, (I), is a ®ve-coordinate compound as the phenanthroline (phen) adduct. The CuIIatom is coordinated by the two N atoms of a phen ligand and the two O atoms of a picolinateN-oxide anion, these atoms forming the basal plane; one O atom of the nitrate group occupies the apical position. The distances involving the Cu atom are comparable with those found in, for example, [Cu(phen)(ox)(H2O)]H2O (Chenet al., 2001) and [Cu(phen)(gly)(Cl)]H2O (Solanset al., 1988). The CuÐOnitrate bond distance is signi®cantly longer than the other CuÐO bond distances, since the O atom of the nitrate occupies the apical position. Both the heterocycle and the anion are planar. The CuIIatom lies out of the basal plane by 0.1456 (5) AÊ in the direction of atom O4.
Experimental
To a solution of Cu(NO3)23H2O (242 mg, 1 mmol) and 1,10-phenanthroline (180 mg, 1 mmol) in ethanol (20 ml) was added a solution of picolinic acid N-oxide (139 mg, 1 mmol) in
furan (10 ml). The resulting solution was stirred for 4 h at room temperature. Crystals of (I) suitable for X-ray analysis were obtained after several days. Analysis found: C 48.56, H 2.57, N 12.86%; calculated for C18H12CuN4O6: C 48.71, H 2.73, N 12.62%.
Crystal data
[Cu(C6H4NO3)(NO3)(C12H8N2)]
Mr= 443.86
Monoclinic,P21=c
a= 9.2861 (11) AÊ
b= 9.5829 (12) AÊ
c= 18.438 (3) AÊ
= 90.750 (4)
V= 1640.7 (4) AÊ3
Z= 4
Dx= 1.797 Mg m 3
MoKradiation Cell parameters from 6799
re¯ections
= 3.1±27.4
= 1.38 mm 1
T= 298(2) K Block, blue
0.380.240.16 mm
Data collection
Rigaku R-AXIS RAPID IP diffractometer
Oscillation scans
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)
Tmin= 0.678,Tmax= 0.8 02 6799 measured re¯ections
3713 independent re¯ections 2699 re¯ections withI> 2(I)
Rint= 0.033 max= 27.4
h= 11!12
k= 12!12
l= 23!23
Refinement
Re®nement onF2
R[F2> 2(F2)] = 0.034
wR(F2) = 0.079
S= 0.91 3713 re¯ections 262 parameters
H-atom parameters constrained
w= 1/[2(F
o2) + (0.0434P)2]
whereP= (Fo2+ 2Fc2)/3
(/)max= 0.001
max= 0.39 e AÊ 3
min= 0.47 e AÊ 3
Table 1
Selected geometric parameters (AÊ,).
Cu1ÐO1 1.8962 (16)
Cu1ÐO2 1.9018(16)
Cu1ÐO4 2.2839 (16)
Cu1ÐN2 2.0113 (19)
Cu1ÐN3 2.0090 (19)
O1ÐCu1ÐO2 93.78(7)
O1ÐCu1ÐO4 104.56 (7)
O1ÐCu1ÐN2 165.37 (7)
O1ÐCu1ÐN3 88.42 (7)
O2ÐCu1ÐO4 93.64 (7)
O2ÐCu1ÐN2 93.47 (7)
O2ÐCu1ÐN3 170.52 (7)
O4ÐCu1ÐN2 87.63 (7)
O4ÐCu1ÐN3 94.73 (7)
N2ÐCu1ÐN3 82.45 (7)
H atoms were placed at calculated positions and re®ned using a riding model, with CÐH distances in the range 0.93±0.96 AÊ and with Uiso(H) = 1.2Ueq(C).
Data collection:RAPID-AUTO (Rigaku, 2001); cell re®nement: RAPID-AUTO; data reduction:RAPID-AUTO; program(s) used to solve structure: SHELXS97(Sheldrick, 1990); program(s) used to re®ne structure:SHELXL97(Sheldrick, 1997); molecular graphics: XP(Siemens, 1994); software used to prepare material for publica-tion:SHELXTL(Siemens, 1995).
References
Chen, X. F., Cheng, P., Liu, X., Zhao, B., Liao, D. Z., Yan, S. P. & Jiang, Z. H. (2001).Inorg. Chem.40, 2652±2659.
Higashi, T. (1995).ABSCOR.Rigaku Corporation, Tokyo, Japan.
Mao, J. G., Zhang, H. J., Ni, J. Z. & Mak, T. C. W. (1998).J. Chem. Crystallogr. 28, 413±418.
Rigaku (2001).RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Sheldrick, G. M. (1990).Acta Cryst.A46, 467±473.
Sheldrick, G. M. (1997).SHELXL97. University of GoÈttingen, Germany. Siemens (1994).XP.Version 5.03. Siemens Analytical X-ray Instruments Inc.,
Madison, Wisconsin, USA.
Siemens (1995).SHELXTL.Version 5.0. Siemens Analytical X-ray Instru-ments Inc., Madison, Wisconsin, USA.
Solans, X., Ruiz-Ramirez, L., Martinez, A., Gasque, L. & Brianso, J. L. (1988).
Acta Cryst.C44, 628±631.
Yan, L., Liu, J. M., Wang, X., Yang, R. D. & Song, F. L. (1995).Polyhedron,14, 3543±3548.
Figure 1
supporting information
sup-1
Acta Cryst. (2005). E61, m441–m442
supporting information
Acta Cryst. (2005). E61, m441–m442 [https://doi.org/10.1107/S1600536805002515]
(Nitrato-
κ
O
)(1,10-phenanthroline-
κ
2N,N
′
)(picolinato
N
-oxide-κ
2O,O
′
)copper(II)
Lei Gou, Xiong-Wei Qu, Bo Zheng, Dao-Yong Wang and Huai-Ming Hu
(Nitrato-κO)(1,10-phenanthroline-κ2N,N′)(picolinato N-oxide- κ2O,O′)copper(II)
Crystal data
[Cu(C6H4NO3)(NO3)(C12H8N2)]
Mr = 443.86 Monoclinic, P21/c
a = 9.2861 (11) Å
b = 9.5829 (12) Å
c = 18.438 (3) Å
β = 90.750 (4)°
V = 1640.7 (4) Å3
Z = 4
F(000) = 900
Dx = 1.797 Mg m−3
Mo Kα radiation, λ = 0.71073 Å Cell parameters from 6799 reflections
θ = 3.1–27.4°
µ = 1.38 mm−1
T = 298 K Block, blue
0.38 × 0.24 × 0.16 mm
Data collection
Rigaku R-AXIS RAPID IP diffractometer
Radiation source: rotating anode Graphite monochromator oscillation scans
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)
Tmin = 0.678, Tmax = 0.802
6799 measured reflections 3713 independent reflections 2699 reflections with I > 2σ(I)
Rint = 0.033
θmax = 27.4°, θmin = 3.1°
h = −11→12
k = −12→12
l = −23→23
Refinement
Refinement on F2
Least-squares matrix: full
R[F2 > 2σ(F2)] = 0.034
wR(F2) = 0.079
S = 0.91 3713 reflections 262 parameters 0 restraints
Primary atom site location: structure-invariant direct methods
Secondary atom site location: difference Fourier map
Hydrogen site location: inferred from neighbouring sites
H-atom parameters constrained
w = 1/[σ2(F
o2) + (0.0434P)2]
where P = (Fo2 + 2Fc2)/3
(Δ/σ)max = 0.001
Δρmax = 0.39 e Å−3
Δρmin = −0.47 e Å−3
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x y z Uiso*/Ueq
Cu1 0.66658 (3) 0.59025 (3) 0.453019 (14) 0.02234 (9)
N2 0.50419 (19) 0.7284 (2) 0.45946 (10) 0.0230 (4) N3 0.66362 (19) 0.60701 (19) 0.56160 (10) 0.0222 (4)
N4 0.9079 (2) 0.7727 (2) 0.38519 (11) 0.0288 (5)
O1 0.79083 (18) 0.43446 (17) 0.46404 (8) 0.0300 (4)
O2 0.63850 (17) 0.56135 (17) 0.35177 (8) 0.0276 (4)
O3 0.7050 (2) 0.4924 (2) 0.24319 (9) 0.0485 (6)
O4 0.81773 (17) 0.77543 (17) 0.43708 (9) 0.0298 (4)
O5 0.9285 (3) 0.8807 (2) 0.35122 (14) 0.0711 (8)
O6 0.9709 (2) 0.66392 (19) 0.36937 (10) 0.0388 (5)
C1 0.7146 (3) 0.4877 (3) 0.30903 (13) 0.0267 (5)
C2 0.8245 (2) 0.3827 (2) 0.33891 (12) 0.0232 (5)
C3 0.8962 (3) 0.2983 (2) 0.28963 (13) 0.0264 (5)
H3A 0.8771 0.3087 0.2403 0.032*
C4 0.9949 (3) 0.1998 (3) 0.31236 (13) 0.0305 (6)
H4A 1.0406 0.1424 0.2791 0.037*
C5 1.0241 (3) 0.1882 (3) 0.38572 (14) 0.0329 (6)
H5A 1.0909 0.1229 0.4023 0.039*
C6 0.9555 (3) 0.2724 (3) 0.43404 (13) 0.0292 (6)
H6A 0.9775 0.2655 0.4833 0.035*
C7 0.4230 (3) 0.7838 (3) 0.40753 (13) 0.0267 (5)
H7A 0.4359 0.7541 0.3601 0.032*
C8 0.3186 (3) 0.8854 (2) 0.42103 (13) 0.0286 (6)
H8A 0.2630 0.9217 0.3832 0.034*
C9 0.2990 (3) 0.9309 (2) 0.49068 (13) 0.0271 (5)
H9A 0.2301 0.9986 0.5003 0.032*
C10 0.3836 (2) 0.8749 (2) 0.54779 (12) 0.0240 (5)
C11 0.3709 (2) 0.9136 (3) 0.62238 (12) 0.0262 (5)
H11A 0.3042 0.9812 0.6354 0.031*
C12 0.4545 (2) 0.8531 (2) 0.67456 (12) 0.0249 (5)
H12A 0.4453 0.8814 0.7225 0.030*
C13 0.5565 (2) 0.7466 (2) 0.65719 (12) 0.0243 (5)
C14 0.6439 (2) 0.6758 (2) 0.70823 (13) 0.0265 (5)
H14A 0.6399 0.6990 0.7571 0.032*
C15 0.7347 (3) 0.5727 (2) 0.68552 (13) 0.0287 (6)
H15A 0.7905 0.5236 0.7191 0.034*
C16 0.7434 (3) 0.5412 (3) 0.61153 (13) 0.0255 (5)
H16A 0.8069 0.4721 0.5968 0.031*
C17 0.5708 (2) 0.7077 (2) 0.58373 (12) 0.0215 (5)
C18 0.4837 (2) 0.7724 (2) 0.52883 (12) 0.0232 (5)
Atomic displacement parameters (Å2)
U11 U22 U33 U12 U13 U23
supporting information
sup-3
Acta Cryst. (2005). E61, m441–m442
O1 0.0418 (10) 0.0296 (10) 0.0188 (8) 0.0113 (8) 0.0060 (7) −0.0008 (7) O2 0.0302 (9) 0.0320 (10) 0.0207 (8) 0.0092 (7) 0.0005 (7) −0.0024 (7) O3 0.0623 (13) 0.0648 (14) 0.0184 (9) 0.0332 (11) −0.0001 (9) −0.0028 (9) O4 0.0353 (10) 0.0279 (9) 0.0266 (9) −0.0046 (8) 0.0097 (7) −0.0022 (8) O5 0.1004 (19) 0.0323 (12) 0.0823 (18) 0.0106 (12) 0.0601 (15) 0.0173 (12) O6 0.0436 (11) 0.0305 (10) 0.0424 (11) 0.0127 (9) 0.0116 (9) 0.0024 (9) C1 0.0298 (13) 0.0271 (13) 0.0232 (12) 0.0023 (11) 0.0002 (10) 0.0002 (11) C2 0.0253 (12) 0.0216 (13) 0.0227 (12) −0.0019 (10) 0.0034 (9) 0.0007 (10) C3 0.0287 (13) 0.0266 (13) 0.0239 (12) −0.0019 (10) 0.0025 (10) −0.0004 (10) C4 0.0293 (13) 0.0289 (14) 0.0334 (14) 0.0037 (11) 0.0083 (11) −0.0038 (12) C5 0.0314 (14) 0.0278 (13) 0.0394 (15) 0.0063 (11) 0.0028 (11) 0.0042 (12) C6 0.0312 (13) 0.0296 (13) 0.0267 (13) 0.0038 (11) −0.0006 (10) 0.0061 (11) C7 0.0301 (13) 0.0303 (14) 0.0197 (12) −0.0001 (11) 0.0026 (10) −0.0006 (10) C8 0.0326 (13) 0.0271 (14) 0.0262 (13) 0.0007 (11) 0.0021 (10) 0.0031 (11) C9 0.0280 (13) 0.0254 (13) 0.0278 (12) 0.0018 (10) 0.0041 (10) 0.0004 (11) C10 0.0264 (12) 0.0208 (12) 0.0248 (12) −0.0034 (9) 0.0056 (10) 0.0016 (10) C11 0.0290 (12) 0.0247 (12) 0.0251 (12) −0.0016 (11) 0.0077 (9) −0.0048 (11) C12 0.0292 (13) 0.0269 (12) 0.0186 (12) −0.0055 (10) 0.0056 (10) −0.0032 (10) C13 0.0263 (12) 0.0240 (12) 0.0227 (12) −0.0069 (10) 0.0052 (9) −0.0009 (10) C14 0.0306 (13) 0.0301 (13) 0.0187 (11) −0.0056 (11) 0.0013 (10) −0.0017 (10) C15 0.0327 (13) 0.0280 (14) 0.0253 (12) −0.0038 (11) −0.0015 (10) 0.0060 (11) C16 0.0288 (12) 0.0233 (12) 0.0243 (12) −0.0001 (10) 0.0018 (10) 0.0017 (10) C17 0.0236 (12) 0.0198 (12) 0.0212 (11) −0.0042 (9) 0.0027 (9) 0.0000 (10) C18 0.0278 (12) 0.0208 (12) 0.0210 (12) −0.0054 (10) 0.0060 (9) 0.0002 (10)
Geometric parameters (Å, º)
Cu1—O1 1.8962 (16) C5—C6 1.365 (3)
Cu1—O2 1.9018 (16) C5—H5A 0.9300
Cu1—O4 2.2839 (16) C6—H6A 0.9300
Cu1—N2 2.0113 (19) C7—C8 1.398 (3)
Cu1—N3 2.0090 (19) C7—H7A 0.9300
N1—O1 1.332 (2) C8—C9 1.371 (3)
N1—C2 1.358 (3) C8—H8A 0.9300
N1—C6 1.361 (3) C9—C10 1.411 (3)
N2—C7 1.322 (3) C9—H9A 0.9300
N2—C18 1.363 (3) C10—C18 1.400 (3)
N3—C16 1.333 (3) C10—C11 1.431 (3)
N3—C17 1.360 (3) C11—C12 1.358 (3)
N4—O5 1.226 (3) C11—H11A 0.9300
N4—O6 1.232 (2) C12—C13 1.432 (3)
N4—O4 1.280 (2) C12—H12A 0.9300
O2—C1 1.278 (3) C13—C14 1.409 (3)
O3—C1 1.217 (3) C13—C17 1.413 (3)
C1—C2 1.531 (3) C14—C15 1.368 (3)
C2—C3 1.393 (3) C14—H14A 0.9300
C3—C4 1.377 (3) C15—C16 1.401 (3)
C4—C5 1.381 (3) C16—H16A 0.9300
C4—H4A 0.9300 C17—C18 1.429 (3)
O1—Cu1—O2 93.78 (7) N1—C6—C5 120.4 (2)
O1—Cu1—O4 104.56 (7) N1—C6—H6A 119.8
O1—Cu1—N2 165.37 (7) C5—C6—H6A 119.8
O1—Cu1—N3 88.42 (7) N2—C7—C8 122.7 (2)
O2—Cu1—O4 93.64 (7) N2—C7—H7A 118.6
O2—Cu1—N2 93.47 (7) C8—C7—H7A 118.6
O2—Cu1—N3 170.52 (7) C9—C8—C7 119.3 (2)
O4—Cu1—N2 87.63 (7) C9—C8—H8A 120.4
O4—Cu1—N3 94.73 (7) C7—C8—H8A 120.4
N2—Cu1—N3 82.45 (7) C8—C9—C10 119.9 (2)
O1—N1—C2 124.92 (19) C8—C9—H9A 120.0
O1—N1—C6 113.68 (18) C10—C9—H9A 120.0
C2—N1—C6 121.4 (2) C18—C10—C9 116.4 (2)
C7—N2—C18 118.0 (2) C18—C10—C11 119.0 (2)
C7—N2—Cu1 129.98 (16) C9—C10—C11 124.5 (2)
C18—N2—Cu1 111.91 (15) C12—C11—C10 121.1 (2)
C16—N3—C17 118.50 (19) C12—C11—H11A 119.4
C16—N3—Cu1 129.48 (16) C10—C11—H11A 119.4
C17—N3—Cu1 111.89 (15) C11—C12—C13 121.3 (2)
O5—N4—O6 121.0 (2) C11—C12—H12A 119.4
O5—N4—O4 118.2 (2) C13—C12—H12A 119.4
O6—N4—O4 120.8 (2) C14—C13—C17 116.9 (2)
N1—O1—Cu1 125.90 (13) C14—C13—C12 124.8 (2)
C1—O2—Cu1 128.02 (16) C17—C13—C12 118.3 (2)
N4—O4—Cu1 119.29 (14) C15—C14—C13 119.7 (2)
O3—C1—O2 124.2 (2) C15—C14—H14A 120.2
O3—C1—C2 115.0 (2) C13—C14—H14A 120.2
O2—C1—C2 120.8 (2) C14—C15—C16 119.8 (2)
N1—C2—C3 118.1 (2) C14—C15—H15A 120.1
N1—C2—C1 123.9 (2) C16—C15—H15A 120.1
C3—C2—C1 118.0 (2) N3—C16—C15 122.1 (2)
C4—C3—C2 121.4 (2) N3—C16—H16A 118.9
C4—C3—H3A 119.3 C15—C16—H16A 118.9
C2—C3—H3A 119.3 N3—C17—C13 122.9 (2)
C3—C4—C5 118.3 (2) N3—C17—C18 116.8 (2)
C3—C4—H4A 120.8 C13—C17—C18 120.3 (2)
C5—C4—H4A 120.8 N2—C18—C10 123.6 (2)
C6—C5—C4 120.3 (2) N2—C18—C17 116.5 (2)
C6—C5—H5A 119.8 C10—C18—C17 120.0 (2)
